Cu(I)-catalyzed asymmetric allylation of ketones and ketimines

Pure and Applied Chemistry

Volumn 80, Issue 5, 2008, Pages 1055-1062

  Kanai, Motomu ^a   Wada, Reiko ^a   Shibuguchi, Tomoyuki ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

Allylation; Asymmetric catalysis; Copper; Ketimines; Ketones; Tetrasubstituted carbon

Indexed keywords

EID: 44649186145     PISSN: 00334545     EISSN: None     Source Type: Journal    
DOI: 10.1351/pac200880051055     Document Type: Conference Paper

References (29)

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12. For a catalytic asymmetric allylation of ketones using allylboronates, see: R. Wada, K. Oisaki, M. Kanai, M. Shibasaki. J. Am. Chem. Soc 126, 8910 (2004).
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14. (b) M. Wadamoto, H. Yamamoto. J. Am. Chem. Soc. 127, 14556 (2005).
15. For an organo-catalytic asymmetric allylation of ketones, see: S. Lou, P. N. Moquist, S. E. Schaus. J. Am. Chem. Soc. 128, 12660 (2006).
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18. 3 is a stable, isolable, and well-defined CuF species. See: D. J. Gulliver, W. Levason, M. Webster. Inorg. Chim. Acta 52, 153 (1981).
19. Direct spectroscopic observation of allylcopper was not possible.
20. For a recent paper discussing metallotropic equilibrium of allyllic metal compounds, see: G. Sklute, I. Marek. J. Am. Chem. Soc. 128, 4642 (2006).
21. This idea is supported by the fact that the linear product was the only observed isomer (46 % yield) in the Cu-catalyzed crotylation of a bulky ketone, t-butyl methyl ketone, using (E)- and (Z)-2.
22. AgF-catalyzed allylation of aromatic aldehydes is significantly faster than that of aliphatic aldehydes. See: A. Yanagisawa, H. Kageyama, Y. Nakatsuka, K. Asakawa, Y. Matsumoto, H. Yamamoto. Angew. Chem., Int. Ed. 38, 3701 (1999).
23. K. C. Nicolaou, C. J. N. Mathison, T. Montagnon. J. Am. Chem. Soc 126, 5192 (2004).
24. iPr did not catalyze the allylation reaction in the absence of Cu.
25. iPr.
26. Y. Suto, R. Tsuji, M. Kanai, M. Shibasaki. Org. Lett. 7, 3757 (2005). Halides other than fluoride sometimes have detrimental effects in Cu(I)-catalyzed reactions, possibly due to their high affinity to Cu(I).
27. tBu, see: T. Tsuda, T. Hashimoto, T. Saegusa. J. Am. Chem. Soc. 94, 658 (1972).
28. iPr).
29. tBu (5 mg, 0.048 mmol) were dissolved in DMF (0.18 mL), and the mixture was stirred at room temperature for 15 min. After cooling to -40°C, allylboronate (121 μL, 0.64 mmol) and a ketone (0.533 mmol) were added successively. The reaction was monitored by TLC, and quenched with 10 % citric acid after the starting material was completely consumed.